Electrically Tunable Single Polaritonic Quantum Dot at Room Temperature.

Exciton-polaritons confined in plasmonic cavities are hybridized light-matter quasiparticles, with distinct optical characteristics compared to plasmons and excitons alone. Here, we demonstrate the electric tunability of a single polaritonic quantum dot operating at room temperature in electric-field tip-enhanced strong coupling spectroscopy. For a single quantum dot in the nanoplasmonic tip cavity with variable dc local electric field, we dynamically control the Rabi frequency with the corresponding polariton emission, crossing weak to strong coupling. We model the observed behaviors based on the quantum confined Stark effect in the strong coupling regime.

Tip-Induced Strain Engineering of a Single Metal Halide Perovskite Quantum Dot.

Strain engineering of perovskite quantum dots (pQDs) enables widely tunable photonic device applications. However, manipulation at the single-emitter level has never been attempted. Here, we present a tip-induced control approach combined with tip-enhanced photoluminescence (TEPL) spectroscopy to engineer strain, bandgap, and the emission quantum yield of a single pQD. Single CsPbBrxI3-x pQDs are clearly resolved through hyperspectral TEPL imaging with ∼10 nm spatial resolution. The plasmonic tip then directly applies pressure to a single pQD to facilitate a bandgap shift up to ∼62 meV with Purcell-enhanced PL increase as high as ∼105 for the strain-induced pQD. Furthermore, by systematically modulating the tip-induced compressive strain of a single pQD, we achieve dynamical bandgap engineering in a reversible manner. In addition, we facilitate the quantum dot coupling for a pQD ensemble with ∼0.8 GPa tip pressure at the nanoscale estimated theoretically. Our approach presents a strategy to tune the nano-opto-electro-mechanical properties of pQDs at the single-crystal level.

Origin of the Stability and Transition from Anionic to Cationic Surface Ligand Passivation of All-Inorganic Cesium Lead Halide Perovskite Nanocrystals.

Recently, the structural stability of all-inorganic halide perovskite nanocrystals has been significantly enhanced. To understand the enhancement, we developed surface-passivation models for cubic CsPbBr3 nanocrystals with anionic (oleate) and cationic (oleylammonium) organic ligands based on first-principles calculations and nuclear magnetic resonance investigations. We propose that the (100) surface is initially terminated with oleate ligand complexes on PbBr2(100) surfaces. Also, the ligand transition to oleylammonium on the Pb-rich surfaces is expected due to the addition of metal halides (ZnBr2) during colloidal synthesis. The significant improvement in the structural stability of the cationic ligand-passivated CsPbBr3 nanocrystals was attributed to the suppressed exposure of the merging-vulnerable (110) surface, caused by the large difference in formation energy between the ligand-passivated (100) and Br-passivated (110) surfaces.

A relationship between the surface composition and spectroscopic properties of cesium lead bromide (CsPbBr3) perovskite nanocrystals: focusing on photoluminescence efficiency.

We have previously developed CsPbBr3 NCs exhibiting a tremendously high photoluminescence (PL) and structural stability by adding ZnBr2. However, understanding of these outstanding properties is lacking due to the absence of spectroscopic analyses, such as spectral or dynamical characteristics. In this work, we conducted a comparative analysis of photophysical properties for conventional-CsPbBr3 NCs and ZnBr2-CsPbBr3 NCs. First, we analyzed the blinking traces by comparing the single crystal PL intermittency. It has been found that the PL quantum yield of CsPbBr3 NCs is gradually decreasing at the ensemble level, resulting from a significant activation of the Auger-induced blinking. Furthermore, the time-resolved TA dynamics supports the fact that Auger-type energy transfer accelerates the hot carrier cooling time, and thereby the Auger-induced blinking behavior in the band-edge state becomes dominant over time. Here, ZnBr2-CsPbBr3 NCs showed a low multiexciton Auger amplitude and therefore had a stable PL emission compared with conventional-CsPbBr3 NCs. Finally, we suggest that both NCs differ in intraband spacing possibly due to capping ligands, finally leading to a suppressed Auger process and higher stability for ZnBr2-CsPbBr3 NCs.

Continuous Purification of Colloidal Quantum Dots in Large-Scale Using Porous Electrodes in Flow Channel.

Colloidal quantum dots (QDs) afford huge potential in numerous applications owing to their excellent optical and electronic properties. After the synthesis of QDs, separating QDs from unreacted impurities in large scale is one of the biggest issues to achieve scalable and high performance optoelectronic applications. Thus far, however, continuous purification method, which is essential for mass production, has rarely been reported. In this study, we developed a new continuous purification process that is suitable to the mass production of high-quality QDs. As-synthesized QDs are driven by electrophoresis in a flow channel and captured by porous electrodes and finally separated from the unreacted impurities. Nuclear magnetic resonance and ultraviolet/visible/near-infrared absorption spectroscopic data clearly showed that the impurities were efficiently removed from QDs with the purification yield, defined as the ratio of the mass of purified QDs to that of QDs in the crude solution, up to 87%. Also, we could successfully predict the purification yield depending on purification conditions with a simple theoretical model. The proposed large-scale purification process could be an important cornerstone for the mass production and industrial use of high-quality QDs.

Air-Stable PbSe Nanocrystals Passivated by Phosphonic Acids.

We developed a new chemical strategy to enhance the stability of lead selenide nanocrystals (PbSe NCs) against oxidation through the surface passivation by P-O- moieties. In the synthesis of PbSe NCs, tris(diethylamino)phosphine (TDP) selenide (Se) was used as a Se precursor, and the resulting PbSe NCs withstood long-term air exposure while showing nearly no sign of oxidation. Nuclear magnetic resonance (NMR) spectroscopy reveals that TDP derivatives passivate the surface of PbSe NC. Through a series of ligand cleavage reactions, we found that the TDP derivatives are bound on NC surface through the P-O- moiety. Based on such understanding, it turned out that direct addition of various PAs during the synthesis of PbSe NCs also results in the NCs whose absorption spectrum remains nearly intact after air exposure for weeks. The P-O- moieties render the NCs stable in the operation of field effect transistors, suggesting that our findings can enable the use of air stable PbSe NCs in wider array of optoelectronic applications.

Ultrastable PbSe nanocrystal quantum dots via in situ formation of atomically thin halide adlayers on PbSe(100).

The fast degradation of lead selenide (PbSe) nanocrystal quantum dots (NQDs) in ambient conditions impedes widespread deployment of the highly excitonic, thus versatile, colloidal NQDs. Here we report a simple in situ post-synthetic halide salt treatment that results in size-independent air stability of PbSe NQDs without significantly altering their optoelectronic characteristics. From TEM, NMR, and XPS results and DFT calculations, we propose that the unprecedented size-independent air stability of the PbSe NQDs can be attributed to the successful passivation of under-coordinated PbSe(100) facets with atomically thin PbX2 (X = Cl, Br, I) adlayers. Conductive films made of halide-treated ultrastable PbSe NQDs exhibit markedly improved air stability and behave as an n-type channel in a field-effect transistor. Our simple in situ wet-chemical passivation scheme will enable broader utilization of PbSe NQDs in ambient conditions in many optoelectronic applications.

Metal tips on pyramid-shaped PbSe/CdSe/CdS heterostructure nanocrystal photocatalysts: study of Ostwald ripening and core/shell formation.

We report ripening of metal particles anchored on pyramid-shaped heterostructure nanocrystals. The 'intra-particle' ripening results in a large metal tip at one corner with the other three tips vanishing. Investigation reveals that the ripening and core/shell formation affects photocatalytic activities via the Fermi level change.